ISSN 20702051, Protection of Metals and Physical Chemistry of Surfaces, 2010, Vol. 46, No. 1, pp. 3239.

Pleiades Publishing, Ltd., 2010.

Original Russian Text D.A. Kudryashov, S.N. Grushevskaya, O.Olalekan, N.V. Kukhareva, A.V. Vvedenskii, 2010, published in Fizikokhimiya Poverkhnosti i Zashchita Materia
lov, 2010, Vol. 46, No. 1, pp. 2835.

PHYSICOCHEMICAL PROCESSES
AT THE INTERFACES

Effect of Orientation of Crystal Face of Silver and its Alloying

with Gold on Properties of Thin Anodic Ag(I) Oxide Films:
II. Photopotential
D. A. Kudryashov, S. N. Grushevskaya, O. Olalekan, N. V. Kukhareva, and A. V. Vvedenskii
Voronezh State University, Universitetskaya pl. 1, Voronezh, 394006 Russia
email: avved@chem.vsu.ru
Received September 5, 2008

AbstractThe current efficiency of the formation of anodic oxide on polycrystalline silver is shown to decrease
with an increase in the concentration of KOH solutions, while the ratelimiting stage remains the solidphase mass
transfer. Photopotential in nanosize Ag(I) oxide films anodically formed on polycrystalline silver is independent of
the OH ion concentration, which means that a photoresponse is generated in the bulk oxide. The ntype conduc
tivity of oxide films on silver, AgAu alloys, and lowindex silver crystal faces, which was determined previously
when measuring photocurrent, is confirmed. Replacing polycrystalline silver with its monocrystals results in a sub
stantial decrease in the photopotential amplitude due to the decrease in the deviation from a stoichiometric compo
sition. The electron mobility and the partial electronic photoconductivity in the anodic Ag(I) oxide depend on the
orientatinon of the crystal face in silver and the gold content. At E = 0.56 V, a series of changes in these characteristics
correlates to the changes in other structuredependent parameters of Ag2O oxide (the optical absorption coefficient
, the concentration of donor defects ND, the width of the spatial charge region W, and the Debye screening
length LD).
DOI: 10.1134/S2070205110010041

INTRODUCTION EC = 0.3 eV (with respect to the zero Fermi level), which

Some peculiarities of the anodic formation of nano
size anodic films of Ag(I) oxide on polycrystalline silver,
AgAu alloys, and lowindex monocrystalline silver faces
in 0.1 M KOH were considered in previous paper [1]. The
kind of conductivity of the oxide film, as well as the roles of
the silver crystal face orientation, the concentration of
gold, and the formation potential of the film in the forma
tion of the structuredependent characteristics of the film
are determined.
The results obtained can substantially be supplemented
and confirmed with the use of one more structuresensitive
in situ technique, namely, the spectroscopy of photopo
tential, which is generated in an oxide film when it is irra
diated with ultraviolet light. Here, it is important to accu
rately determine whether the photoresponse originates in
the oxide film or at the oxidesolution interface. Only the
photoresponse of the bulk semiconductive layer provides
information about the electronic structure, type of con
ductivity, and other parameters of the layer.
Numerous data about the properties of the anodically
formed semiconductive Ag(I) oxide, particularly its type of
conductivity and the width of the band gap, are contradic
tory. According to [25], Ag(I) oxide involves oxygen
vacancies at the crystal lattice points and, hence, acts as an
ntype semiconductor. Quantum mechanical calculations
[3] provided an estimate of the top of the valence band
EV = 1.0 eV and the bottom of the conductivity band
means that the band gap is Ebg = 1.3 eV. Changes in the
conditions of Ag2O production can change the amount of
defects and their nature and, hence, the kind of conductiv
ity. For example, indications of ptype silver oxide conduc
tivity are given in [6, 7]. Accordingly, the Ebg band gap
1
changes from 1.21.5 eV [2, 4, 6, 7] to 2.2 eV [5, 8]. It is
quite possible that the differences between the results
obtained by different authors are determined by the insuf
ficient control over the conditions of nucleation and
growth of the oxide phase.
A principally important problem of the contribution
provided by the surface (adsorption) energetic states,
which can noticeably affect the photoresponse of the
nanosize oxide film, remains unsolved yet. One of the cri
teria of the photoresponse generation due to the prevailing
electronhole transitions between the bulk rather than
surface states is the sensitivity of the photopotential to the
chemical and microstructural state of the silver surface
and, by contrast, its independence of the properties of the
aqueous solution, particularly, of the OH content.
Despite the obvious significance of this factor in the anodic
formation of Ag(I) oxide in an alkaline environment, the
role of OH concentration was not practically studied in
the in situ photoelectrochemical experiments. Let us note
that these experiments should be carried out very accu
1 Depending on the thickness of Ag(I) oxide.

32
 EFFECT OF ORIENTATION OF CRYSTAL FACE OF SILVER
E = ED + Eph
EC
Pt(Pt)
h 0.6
EV
Working
electrode
Lp W 7
L 8
Fig. 1. Scheme of photopotential generation and record
ing: ED is dark potential; L is oxidefilm thickness; Lp is
hole diffusion length; W is spatial charge region; EV is top
of the valence band; and EC is bottom of conductivity
band.
rately; one should continuously monitor the thickness of
the anodic film, since changes in the solution concentra
tion and in the potential results in substantial changes,
while the photoresponse of a thin oxide film is sensitive to
size.
The object of this work is to clarify the character of the
effects of OH ion concentration, silver crystal face orienta
tion, silver alloying with gold, and the formation potential
on the regularities of the anodic formation and some struc
turedependent properties of nanosize anodic Ag(I) oxide
films.
EXPERIMENTAL
The working electrodes were pretreated as outlined in
[1]. A deaerated KOH solution with a concentration of 0.1
or 0.5 mol/l was taken as the working enviroment. Electro
chemical measurements were carried out with an IPC
Compact potentiostat. Potentials are given in the standard
hydrogen electrode scale, and the current densities are
recalculated to the visible electrode surface.
When measuring the photopotential (Eph), an experi
mental unit developed in [9] was used. A threeelectrode
cell with a quartz window [1] was supplemented with an
additional Pt(Pt) electrode screened from direct light with
a Teflon shield. The main peculiarities of the photoelectro
chemical measurements are given in detail in the previous
paper. The sole difference is as follows: the photopotential
was measured under conditions of a broken circuit (Fig. 1)
upon switching off the polarization of the grounded elec
trode.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46, No. 1 2010
33
eq E eq
i, mA/cm2 E g O/Ag(0.5OH ) g2O/Ag(0.5OH )
2
1
0
1 K
i, mA/cm2
2
0.8
3
4
0.4 '
5
6 0.2
'
0
E, V
0.4 0.5 0.6
K
0.2 0.3 0.4 0.5 0.6
E, V
Fig. 2. Cyclic voltammograms of polycrystalline silver in
0.1 M KOH (dashed line) and 0.5 M KOH at v = 1 mV/s.
RESULTS AND DISCUSSION
Anodic Formation of Ag(I) Oxide on Polycrystalline Silver
in KOH Solutions of Various Concentrations
The shape of cyclic voltammograms in 0.1 and 0.5 M
KOH solutions is the same overall (Fig. 2). Anodic peak
(A) is preceded by a small prepeak ('), which is assigned
[1015] to the twolayer structure of the anodic Ag(I)
oxide on silver. Compact Ag2O oxide (or AgOH hydrox
ide) forms a thin inner layer, while porous Ag2O oxide
forms the thicker outer layer. The cathodic branch has one
pronounced current peak (C).
A comparative analysis of the voltammograms
recorded in solutions with different KOH concentrations
shows that the total polarization current is much higher in
the more concentrated solution at all the potentials of the
iE curve. However, taking into account that several
anodic partial processes can take place concurrently (as
was noticed in the previous paper), the increase in the cur
rent may be caused by an increase in the rates of oxide for
mation and active silver dissolution at the open surface sites
or via the film pores. Accordingly, the current efficiency of
the oxide formation () and, hence, the thickness of the
oxide film (L) can change depending on the solution con
centration. Experimental cathodic reduction of the anod
ically formed oxide in a fresh 0.5 M KOH solution con
taining no soluble products of silver oxidation enabled us to
determine the current part spent on the formation of the
difficultly soluble silver oxide (Table 1). Compared to
0.1 M KOH solution, the value of decreases by more
than half. The increase in the OH concentration may lead
to the formation of a more porous oxide layer and, hence,
to a noticeable increase in the rate of the active anodic dis
solution of silver.
The formation potentials of the inner (EA') and outer
(EA) oxide layers, as well as the reduction potential of Ag2O
34 KUDRYASHOV et al.

Table 1. Dependence of the current efficiency on the ox about the absence of the hydrodynamic effect on the
ideformation potential on Agpoly electrode in 0.5 M KOH anodic and cathodic peak currents on an Ag electrode in a
(q = 5 mC/cm2) 0.1 M KOH solution, we can conclude that the prevailing
transport limitations of the Ag2O formation and reduction
E, V 0.43 0.45 0.47 0.49 0.51 0.53 in the oxide phase are probably localized in pores. The dif
fusivity cannot be estimated because the nature of the dif
fusing particles is unclear. According to indirect data [17,
, % 15 23 38 28 28 38 18], these particles may be silver cations.

Calculations of the Photopotential

(EC), are shifted in the negative direction with an increase
in the concentration of the alkaline solution. The shift
nearly coincides with the difference between the equilib
rium potentials of the Ag2O formation in 0.1 and 0.5 M
KOH solutions. Thus, the overpotential of the formation
and reduction of Ag(I) oxide does not change in the more
concentrated solution.
In order to determine the nature of the overpotential
more accurately and to clarify the kinetics of the anodic
and cathodic processes, we carried out a series of voltam
metric measurements at various scanning rates of the
potential. When v is increased from 0.2 to 400 mV/s, the
maximum currents of the anodic and cathodic processes
noticeably increase, and the peaks themselves become
more diffuse. Diagnostic criteria of linear voltammetry
given in [16] enable us to determine the character of the
limiting stage from the basic parameters of the iE curves.
For example, if the ratedetermining stage of the forma
tion or reduction of the oxidation products is the bulk dif
fusion, the peak current should be proportional to the
square root of the scanning rate as follows:
i = k v1/2. (1)
Processing the data of linear voltammetry in the crite
rial coordinates shows that, in fact, the peak currents that
correspond to anodic (' and A) and cathodic (C) maxima
change in proportion to the square root of the scanning
rate (Fig. 3). Taking into account the data of [15, 17, 18]
i, mA/cm2
20
10
0 '
10
20
K E ph = 2kT
30
40
0 5 10 15 20
v1/2, (mV/s)1/2
Fig. 3. Peak currents depending on potential scanning rate.
in Thin Semiconductive Films
In the previous paper, we derived formula (8) for the
photoresponse in semiconductive structures with a thick
ness L, which does not exceed the W width of the spatial
charge region. At the moment when the polarization is
switched off, the iph photocurrent becomes zero. Then,
using the same suppositions, we come to the following
expression for the photopotential in an ntype semicon
ductive film:
kT
E ph =  ln 1
e
ext in L L
f 0 ( 1 R ref ) ( 1 + R ref e ) ( 1 e )
+ 
 (2)
ND Dn
e ( E E fb )
L  e 

2F 
kT
LD .
2L
D
Here, is the inner quantum yield; f is the factor
that takes into account the difference between the
recombination and consumption rates of holes in an
electrochemical reaction at the oxidesolution inter
ext in
face; 0 is the light flux density; R ref and R ref are
the lightflux reflection coefficients of the internal and
external (with respect to the substrate) oxide bound
aries; is the light absorption coefficient, ND is the
bulk concentration of the donor defects; Dn is the dif
fusivity of electrons; LD = (0kT/e2ND)1/2 is the Debye
length; is the dielectric constant of the oxide; is the
oxide formation potential; fb is the flatband poten
in
tial; and F(u) is the Doson integral. Let us set R ref 1
and assume that the second term in square brackets is
small compared to unity. Then, taking into account
that F(u) = 1 and (1 eL) L at L/ 2L D < 1, we
arrive at the simplified expression
ext 2 e ( E E fb )
( 1 R ref )f 0 L 
kT
 
e . (3)
e ND Dn
As follows from Eq. (3), in fairly thin semiconductive
films, the photopotential should be proportional to the
squared film thickness and the light intensity (at small 0
values). In thick films whose thickness exceeds the width of
the spatial charge region, the photopotential is not sensi
tive to size.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46 No. 1 2010

 EFFECT OF ORIENTATION OF CRYSTAL FACE OF SILVER 35

Photopotential of Anodically Formed Ag(I) Oxide E, V

0.60 polarization
When irradiating Ag2O oxide films of different thick switching off
ness that were potentiostatically formed on an Agpoly elec
trode, a negative photopotential is recorded upon switch 0.56
h
ing off the polarization (Fig. 4). This fact confirms the n
type conductivity of Ag(O) oxide. Note that regardless of
the oxide formation potential, the light flux intensity and 0.52 100
s
the anodic charge correspond to the L range of 2200
200 5
nm and the photopotential decreases with time. In this 0.48 ms ms
case, a substantial part of the Epht dependence can be
linearized in coordinates that correspond to the formal
kinetic equation of an irreversible firstorder reaction as 0.44
follows (Fig. 5):
st st 0.40
ln [ E ph ( t ) E ph ] = ln [ E ph ( 0 ) E ph ] kt. (4) 0 100 200 300 t, s
st
Here, Eph(0) and E ph are the photopotential ampli Fig. 4. Chronopotentiogram of an Agpoly electrode in
0.1 M KOH at pulsed UV irradiation at q = 7 mC/cm2,
tudes at the moments when the polarization is = 470 nm, and 0 = 3.56 1015 photon/(cm2 s).
switched off (set as zero) and when the quasistate
2
state level is achieved; k is the rate constant of a par
ticular reaction related to the characteristic time of ext 2 e ( E E fb )
2e 0 f ( 1 R ref )L 
kT

the decay process as follows: = k .
1
E ph 
e , (5)
n
Taking into account the theoretically founded
dependence of the photopotential amplitude on the where
anodic film thickness, we may suppose that the n = enn enND. (6)
decrease in Eph with time is caused by the thinning of Using the optical and structural characteristics of the
the oxide film during the chemical dissolution. In fact, oxide film obtained in [1] from the photoresponse mea
if this process proceeds as a reaction of the first order surements, we estimated the partial electronic conductiv
in oxide, the following differential kinetic equation is ity n from the slope of EL2 dependence (at E = const)
valid: dL/dt = k L. As an additional confirmation, we and calculated the electron mobility n in an Ag2O film
according to Eq. (6) (Table 2). In an oxide of a constant
may consider the nearly accurate coincidence of the thickness formed on polycrystalline silver, the partial elec
characteristic times of the photopotential decay and
the reverse rate constants of the Ag(I) oxide dissolu
1
tion k , which was obtained previously using a rotat ln(Eph ESt
ph ) [Eph, V]
ing disc electrode with a ring [19].
4 Agpoly
The negative sign of the photopotential is also typical of
Ag(I) oxide formed in Ag100, Ag110, and Ag111 monocrys Ag111
tals. The shape of semilogarithmic Epht dependence is Ag110
also the same (Fig. 5). However, the photopotential values 3 Ag100
are smaller in the whole time interval compared to those
recorded on a polycrystalline substrate.
Irrespective of the face orientation, the formation 2
potential, the light flux intensity, and the wavelength, the
photopotential substantially increases with an increase in E = 0.56 V
the thickness of Ag2O oxide film. Here, the experimental 1 q = 5 mC/m2
Eph(0) L2 dependence is linear in complete agreement 0 = 7.12 1015 photon/m2 s
with Eq. (3) (Fig. 6a). The Eph(0) dependence also agrees
with Eq. (3) (Fig. 6b).
Let us rewrite Eq. (3) as follows: 0 100 200 300 t, s

2 The
values of Eph(0) are used below in the analysis of the effects Fig. 5. Photopotential decay with time upon switching off
of diverse factors on the photopotential. polarization.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46, No. 1 2010
36 KUDRYASHOV et al.

Eph(0), V (a) Eph(0), V (b)

160
120 Agpoly Agpoly
Ag100 Ag100
Ag111 120 Ag111
Ag110 Ag110
80
80 q = 5 mC/m2
= 470 nm
40 = 470 nm 40
0 = 7.12 1015 photon/m2 s

0 40 80 120 0 2 4 6 8
L2, nm2 0 1015 photon/m2 s

Fig. 6. Photopotential dependence on (a) thickness of Ag2O film and (b) light flux intensity.

tronic photoconductivity slightly increases with an

increase in the formation potential of the oxide film.
Insofar as the changes in n are much smaller and non
systematic, we may assume that a certain increase in n
with an increase in is related to the increase in the con
centration of donor defects. Note that, at the bipolar pho
toconductivity of an ntype oxide when = p + n, the
prevailing contribution to the summary migration flow in
the spatial charge region, which originates upon the oxide
irradiation, is provided by nonbasic charge carriers. Calcu
lations according to Eq. (5) give n values that cannot be
compared to the bulk conductivity of Ag(I) oxide deter
mined by the basic carriers.
When Ag(I) oxide formed on a polycrystalline substrate
at = 0.56 V is replaced with an oxide of the same thick
ness grown on a monocrystal, the n electronic conductiv
ity slightly decreases, and the n mobility of electrons in the
spatial charge region increases. The series of changes in n
and n at = 0.530.56 V coincides with those found ear
lier (see Eq. (11) in the previous paper) in the case of ,
ND, W, and LD at the same growth potentials of the oxide:
n ( Ag 2 O Ag 100 ) > n ( Ag 2 O Ag 111 )
> n ( Ag 2 O Ag 110 ),
(7)
n ( Ag 2 O Ag 100 ) < n ( Ag 2 O Ag 111 )
< n ( Ag 2 O Ag 110 ).
For the photopotential measurements, silver oxide was
formed on AgAu alloys at the potential of the main vol
tammogram peak, which was not constant, but rather
increased with an increase in the gold content. It turned
out that the photopotential is negative and exponentially
depends on t upon switching off the polarization in all the
cases. The values of n and n (Table 2) were determined
from the linear EphL2 dependence (Fig. 7). An increase in
the gold content in the silver lattice to 4 at % results in a
decrease in the partial electronic photoconductivity n of
the oxide by a factor of more than 20, chiefly due to the
sharp decrease in the electron mobility. An anomalous
increase in n on Ag15Au is scarcely significant, since at
= 0.77 V, the formation of AgO oxide becomes possible.

Table 2. Partial electronic conductivity n and electron mobility n in the anodic Ag(I) oxide

Electrode Agpoly Ag110 Ag100 Ag111 Ag1Au Ag4Au Ag15Au

E, V 0.54 0.55 0.56 0.56 0.58 0.60 0.58 0.60 0.77

n 105, 1 cm1 2.3 3.1 9.8 4.8 2.19 0.43 2.19 0.43 222

n 102, cm2/(V s) 3.21 3.96 2.73 14.5 33.1 53.7 33.1 53.7

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46 No. 1 2010

 EFFECT OF ORIENTATION OF CRYSTAL FACE OF SILVER 37

Eph(0), V In fact, in 0.1 M KOH at a potential of the main anodic

Ag1Au (0.58 V)
200
Ag4Au(0.60 V)
Ag15Au(0.77V)
Agpoly (0.56 V)
100
= 470 nm
0 = 7.12 10 photon/m2 s
15
0 40 80 120
L2, nm2
Fig. 7. Photopotential dependence on thickness of Ag(I)
oxide formed on AgAu alloys.
The photopotential produced in an oxide film anodi
cally formed in a 0.5 M KOH solution on a polycrystalline
silver electrode is negative at all the studied potentials and
charges spent, similar to the situation in 0.1 M KOH. The
photopotential amplitude still increases with an increase in
the charge, and the photopotential decreases with time
upon switching off the polarization, which is caused by the
chemical dissolution of the oxide film and the decrease in
its thickness. However, the photopotential amplitude in
Ag(I) oxide formed in 0.5 M KOH is much smaller on the
whole compared to that recorded in a 0.1 M KOH solution
(Fig. 8). This decrease in the photopotential is probably
caused by the difference in the thicknesses of Ag2O films.
peak EA = 0.56 V, the current efficiency of the oxide for
mation on Agpoly is 83%, while in 0.5 M KOH at EA =
0.53 V, equals 38%; thus, it is nearly 50% smaller at the
same current density (5 mC/cm2). Accordingly, the
oxide film formed in 0.5 M KOH is 50% thinner com
pared to that in 0.1 M KOH; i.e., L [0.1 M KOH]/L
[0.5 M KOH] = 2.1. Taking into account the quadratic
character of the photopotential dependence on L (Eq.
(3)), it can easily be shown that, in the more concentrated
KOH solution, the photopotential should decrease by a
factor of 4.4. The experimentally observed decrease in the
photopotential qualitatively agrees with the theoretically
expected decrease as follows:Eph(0) [0.1
KOH]/Eph(0)[0.5 M KOH] = 3.5 at = 470 nm. This
enables us to conclude that, in Ag2O films of the same
thickness obtained in different alkaline solutions, the pho
topotentials are also the same and independent of the
hydroxideion concentration. Consequently, the photo
potential is generated in the oxide phase and is not related
to the redox processes at the oxidesolution boundary.
This result (along with the pronounced effect of the silver
crystal face orientation, alloying with gold, and the film
thickness on the photopotential values and the structure
dependent characteristics of the anodic Ag(I) oxide) con
firms the idea that the photoresponse is generated in the
bulk of the semiconductive oxide rather than in the surface
levels, while Ag(I) oxide itself is formed chiefly as a result
of the direct electrochemical oxidation rather than accord
ing to the dissolutiondeposition mechanism.
Photopotential Spectroscopy
The spectral dependence of the photopotential in an
Ag2O film formed on polycrystalline silver and its monoc

Eph(0), mV
Eph, V
0 = 3.56 1015 photon/m2 s
100 300
q = 5 mC/m2
0.1 M KOH (E = 0.56 V)
80 Agpoly
Ag111
200 Ag110
60 Ag100

40 100
0.5 M KOH (E = 0.56 V)
20

0
1.5 2.0 2.5 3.0 h, eV
0 100 200 300 400 t, s
828 621 497 414 355
Fig. 8. Decrease in photopotential with time in anodically , nm
formed Ag(I) oxide upon switching off polarization at
0 = 3.56 1015 photon/(cm2s), = 470 nm, and q = Fig. 9. Spectral dependence of photopotential in Ag(I)
5 mC/cm2. oxide obtained on silver in 0.1 M KOH.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46, No. 1 2010
38
[Eph(0)h]2 106, (VeV)2 (a)
1.6
0.1M KOH
1.2 0.5M KOH
0.8
0.4
0 0
1.5 2.0 2.5 3.0
Fig. 10. Spectral dependence of photopotential in coordinates criterial for (a) direct and (b) indirect optical transitions.
rystals has three peaks (Fig. 9). It is important that their
positions are the same as in the photocurrent spectra [1].
The positions of peaks are independent of the concentra
tion of KOH solutions and crystallographic orientation of
the substrate. Accordingly, the nature of the absorption
processes at the corresponding wavelengths is the same.
The central peak is probably related to the selfadmittance,
which enables us to estimate the band gap of the anodically
formed Ag(I) oxide.
According to Eq. (3), photopotential is proportional to
. Taking into account the dependence [20], we
come to a spectral dependence of the photopotential at
L = const, E = const, and 0 = const, which is similar to
that obtained for the photocurrent as follows:
( E ph h )
2/m
= C2 L
4/m
( h E bg ).
Here, Ebg is the band gap; 2 is a coefficient; and m = 1 or
4 for direct and indirect optical transitions, respectively.
Graphically processing the experimental data in the
coordinates that are criterial according to Eq. (8) at differ
ent m values shows that direct optical transitions prevail in
the oxides obtained in both solutions (Fig. 10). Insofar as
the anodic charge was kept the same (q = 5 mC/cm2),
while the current efficiency decreased by nearly half with
an increase in the OH concentration from 0.1 to 0.5 M,
the photopotential amplitude of the oxide formed on a sil
ver electrode in the more concentrated solution is smaller
than in 0.1 M KOH at all the wavelengths.
The Ebg value obtained from the photopotentials of the
oxides formed either on polycrystalline silver or on
monocrystals is 2.09 eV and 1.8 eV in the case of direct and
indirect optical transitions, respectively. The band gap is
independent of the concentration of a potassium hydrox
ide solution.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46 No. 1 2010
KUDRYASHOV et al.
[Eph(0)h1/2, (VeV)1/2 (b)
20
0.08 30
0.06 15
20
0.04 10
10
0.02 5
1.80
h, eV 1.5 2.0 2.5 3.0 h, eV
CONCLUSIONS
1. The rate of the anodic process on polycrystalline sil
ver increases with an increase in the OH concentration;
the nature of the oxideformation overpotential does not
change and corresponds to the solidphase diffusion. The
current efficiency of the oxide formation decreases with an
increase in the OH concentration due to the increase in
the part of the soluble oxidation products.
2. Judging from the sign of photopotential, Ag(I) oxide
has the ntype conductivity. The oxide thickness is smaller
than the width of the spatial charge region, because the
photopotential increases in proportion to the squared film
thickness.
3. As follows from the photopotential independence of
(8) the concentration of aqueous potassium hydroxide solu
tion, the potential is generated in the bulk oxide. This con
clusion is supported by the discovered effect of the crystal
face orientation of silver and the degree of its alloying with
gold. In our opinion, these data confirm the hypothesis
that Ag(I) oxide is formed on silver chiefly as a result of a
direct electrochemical reaction rather than due to the
redeposition from the nearelectrode layer.
4. The decrease in the photopotential when polycrys
talline silver is replaced with silver monocrystals results
from the decrease in the deviation of the oxide film from
the Ag2O stoichiometric composition. An increase in the
formation potential of Ag2O produces an opposite effect;
i.e., the photopotential of a film of the same thickness is
larger.
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